KR20180113360A - Preparation method of filler using micro-cellulose and calcium compound and paper containing filler prepared by the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a filler, the method comprising: (1) a step of fibrillating wood fiber, non-wood fiber, or a mixture thereof with a refiner; (2) a step of passing the fibrillated fiber through a screen, and obtaining fine powder of fine cellulose components having a Canadian standard water solubility of 200 ml or less and having a water retention value (WRV) of 1.5 g/g or more; (3) a step of preparing the fine powder into a solution of 0.2-4.0 wt%, and adding a calcium compound to the solution to be mixed; (4) a step of manufacturing a fine powder and calcium compound composite by adding an ionic polymer to the fine powder solution mixed with the calcium compound; and (5) a step of manufacturing a synthetic composite of fine powder and calcium carbonate by injecting carbon dioxide into the fine powder and calcium compound composite at 30-60°C.

Description

[0001] The present invention relates to a method for preparing a filler using microcellulose and a calcium compound, and a paper comprising the filler for paper produced thereby,

The present invention relates to a method for producing a filler using microcellulose and a calcium compound, and a paper comprising the papermaking filler produced thereby.

The raw materials of the paper are wood pulp, filler and other additives, among which the wood pulp is the main material, followed by the filler. Fillers are used to improve paper quality such as paper opacity, brightness and printability, and on the other hand, since fillers are less expensive than wood pulp, Can be expected.

The addition of calcium carbonate in the production of paper generally improves paper opacity, printability, whiteness, and reduces the cost of paper by reducing the cost of expensive wood pulp, but calcium carbonate is not combined with wood pulp Since the density is higher than that of wood pulp, the more the paper is put, the lower the strength of the paper and the higher the density of the paper. The lowering of the stiffness of the paper caused by the lowering of the strength of the paper or the higher the density of the paper results in a condition that can not contain a lot of calcium carbonate in the paper. Therefore, it is very necessary to develop a technique for keeping the physical properties of paper and containing a lot of calcium carbonate. In this situation, the technique of applying calcium carbonate in the paper making process of paper has been proposed. Recently, calcium carbonate was mixed with fine particle of preflocculation technique or wood pulp, and then fine particles and calcium carbonate were combined using polymer The method used is being used. Although the paper produced using such a technique exhibits relatively high heat shrinkage, it is in fact difficult to incorporate more calcium carbonate into the paper.

On the other hand, Korean Patent No. 1535522 discloses a method for producing a papermaking filler containing nano cellulose and a papermaking filler produced thereby, and Korean Unexamined Patent Publication No. 2002-0094393 discloses a paper comprising lignocellulose The present invention also relates to a method for producing a filler using the microcellulose and a calcium compound of the present invention and a papermaking filler prepared thereby. There is no known paper.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned needs, and it is an object of the present invention to provide a paper comprising a method for producing a filler using microcellulose and a calcium compound and a paper filler produced thereby, The present inventors have completed the present invention by confirming that the paper prepared using one filler has excellent heat fineness, bulk, smoothness, bending stiffness and fold endurance.

In order to achieve the above object, the present invention provides a method for producing a fiber-reinforced composite fiber, comprising: (1) fibrillating a wood fiber, a non-wood fiber or a mixture thereof with a refiner;

(2) passing the fibrillated fiber through a screen to obtain microfine cellulose fine particles having a water standard value of not more than 200 ml and a water retention value of not less than 1.5 g / g of WRV;

(3) preparing the fine particles in a solution of 0.2 to 4.0% by weight, adding a calcium compound to the solution and mixing the solution;

(4) adding an ionic polymer to the solution of the fine particles mixed with the calcium compound to prepare a fine particle and a calcium compound complex; And

(5) a step of injecting carbon dioxide into the microparticles and the calcium compound complex at 30 to 60 ° C to prepare a synthetic composite of fine particles and calcium carbonate.

The present invention also provides a paper comprising the filler produced by the above production method.

The present invention relates to a method for producing a filler using microcellulose and a calcium compound, and a paper comprising the papermaking filler produced thereby. The paper comprising the filler produced by the production method of the present invention is excellent in the use of high-grade paper, in particular, as printing paper, because it has excellent heat shortening, bulk, smoothness, bending stiffness and fold endurance, It is possible to manufacture the semiconductor device of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for producing a filler of the present invention.

(1) fibrillating wood fibers, non-wood fibers or mixtures thereof with a refiner;

(2) passing the fibrillated fiber through a screen to obtain microfine cellulose fine particles having a water standard value of not more than 200 ml and a water retention value of not less than 1.5 g / g of WRV;

(3) preparing the fine particles in a solution of 0.2 to 4.0% by weight, adding a calcium compound to the solution and mixing the solution;

(4) adding an ionic polymer to the solution of the fine particles mixed with the calcium compound to prepare a fine particle and a calcium compound complex; And

(5) a step of injecting carbon dioxide into the fine powder and the calcium compound composite at 30 to 60 ° C to prepare a synthetic composite of fine powder and calcium carbonate.

In the step (1), the wood fiber is a chemical pulp of a softwood, a hardwood or a mixture thereof, and the wood fiber is selected from the group consisting of Abaca pulp, rice straw pulp, red algae pulp, bagasse pulp, bamboo pulp, cotton pulp, Jute pulp, and kenya pulp. However, the present invention is not limited thereto. In the step 1, the refiner refers to a machine used for imparting aptitude as a papermaking raw material, and a valley beater, disk refiner, conical refiner, Jordan engine, stock maker, hydrafainer or rod mill, and may be suitably used according to the purpose.

In the step (2), it is convenient to use the screen to remove the long fibers and to use fine fiber fibers of a uniform size. It is preferable to use a screen of 100 to 500 mesh, more preferably, But is not limited to, using a 300 mesh screen.

In the step (3), the calcium compound is preferably at least one selected from calcium hydroxide, calcium chloride, calcium sulfate and calcium phosphate, but is not limited thereto. When calcium hydroxide is used as the calcium compound, calcium hydroxide produced by hydrating calcium oxide or reacting sodium hydroxide with calcium chloride can be used. That is, since sodium hydroxide and calcium chloride are reacted to form calcium hydroxide, calcium carbonate can be formed by reacting with carbon dioxide even if calcium hydroxide is not directly added.

In the step (3), the mixing ratio of the fine powder and the calcium compound is preferably, but not limited to, the weight ratio of the fine powder to the calcium carbonate in the weight ratio of 1: 1 to 70 after the calcium compound completes the carbonation reaction together with the carbon dioxide, If the weight ratio of the fine powder to the produced calcium carbonate is less than 1: 1, the effect is very small. If the weight ratio is more than 1:70, an excess amount of calcium carbonate that does not adhere to the fine powder is formed.

Light calcium carbonate (PCC) or heavy calcium carbonate (GCC) may be previously attached to the fine powder. At this time, an ionic polymer may be used to adhere the hard calcium carbonate (PCC) or the heavy calcium carbonate (GCC) to the fine powder.

The average particle diameter of the microparticulate and calcium compound composites prepared in step (4) is preferably 5 to 50 μm, but is not limited thereto.

In step (4), the ionic polymer (ionic polymer) is preferably a cationic, anionic, or nonionic polymer. Preferable examples of the cationic polymer include polyacryl amide, polydadmac, polydiallyldimethylammonium chloride, cationic starch, polyethyleneimine or polyamine, and the anionic polymer may be a polyacrylamide, a micro polymer or a mixture thereof. Anionic starch, and nonionic polymers include polyethylene oxide, starch or guar gum, but are not limited thereto.

In the step (5), calcium contained in the calcium compound component is dissolved in the form of a salt such as calcium hydroxide. Calcium carbonate can be synthesized through carbonation by injecting carbon dioxide therein. The temperature at which the carbon dioxide is injected and reacted with the mixture is preferably 30 to 55 ° C. When the temperature is 30 to 60 ° C, most of the calcite crystals are formed. When the temperature is lower than 30 ° C, amorphous vaterlite forms are formed to lower the quality of the paper. When the temperature exceeds 60 ° C, aragonite And thus the strength of the paper is lowered, so that it may not be suitable as a paper filler.

The present invention also relates to a paper comprising a filler prepared by the above process, wherein the paper comprises 1 to 90% by weight of a papermaking filler; And 10 to 99% by weight of natural pulp or regenerated pulp, preferably 10 to 60% by weight of the papermaking filler, but is not limited thereto.

In the present invention, the term length (km) of the paper means a length of paper at a time point when the paper is broken while being increased in load on the test piece as a method of indicating the paper tensile strength.

The bulk (cm ³ / g) means the thickness of the printing paper, and the smoothness (seconds) means smoothness and smoothness of the paper table.

Bending stiffness (gcm) refers to the force required to bend a paper or wood of any length.

Folding endurance refers to the number of times a paper is folded and broken until it is broken, and the higher the number, the higher the degree of theft. This means that the strength is high.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not limited thereto.

Example  One.

a) Hardwood bleaching Chemical pulp was fibrillated by treatment with a valley beater.

b) The fibrillated fiber was passed through a 150 mesh screen to prepare fine cellulose (hereinafter referred to as fine powder) which passed through the screen. The fine particles passing through the screen were found to be less than 200 ml in Canadian standard freeness and 1.5 g / g in WRV.

c) The fine powder was diluted to 1.0% by weight, calcium hydroxide was added to the fine powder so that the weight of the calcium carbonate produced by the carbonation was 30 times as fine as the fine powder (fine powder: calcium carbonate = 1: 30) After mixing, 0.2% of cationic PAM (polyacryl amide) was added in a vortex state to prepare agglomerates (composite of fine particles and calcium compounds).

d) At 40 캜, carbon dioxide was injected into the composite of the above-mentioned fine particles and the calcium compound (calcium hydroxide) to form calcium carbonate in a swirling state to prepare a synthetic composite of fine particles and calcium carbonate.

Example  2

In the c) of Example 1, the same fine particles and calcium carbonate synthesis complex as in Example 1 were prepared, except that the weight ratio of the fine powder and calcium carbonate was 1:50.

Example  3

a) Wood pulp mixed with hardwood chemical pulp by weight ratio of softwood chemical pulp to softwood chemical pulp was defatted by a valley beater so as to have a water content of 500 ml by a Canadian standard freeness measurement method.

b) 30% by weight of the synthetic component of the fine powder and the calcium carbonate prepared in Example 1 was added to the pulp obtained in the above manner to prepare paper having a basis weight of 60 g / m ² .

Example  4

In Example 3 (b), paper was prepared in the same manner as in Example 3 except that 40% by weight of a synthetic composite of a fine powder and calcium carbonate was added.

Example  5

A paper having a basis weight of 60 g / m ² was prepared in the same manner as in Example 3, except that the composite of the fine powder and the calcium carbonate prepared in Example 2 was used.

Example  6

In Example 5, a paper having a basis weight of 60 g / m ² was prepared in the same manner as in Example 5 except that 40% by weight of a synthetic composite of a fine powder and calcium carbonate was used.

Comparative Example  One

The same fine particles and calcium carbonate synthesis complex as in Example 1 were prepared, except that the calcium carbonate was formed at 20 ° C when the calcium carbonate was formed in the vortex state in Example 1 (d).

Comparative Example  2

In Comparative Example 1, d), the same fine powder and calcium carbonate composite composite as in Comparative Example 1 were prepared except that the weight ratio of the prepared fine powder and calcium carbonate was 1:50.

Comparative Example  3

In Example 1 a), a super masscolloid was used instead of a valley beater, and the mixture was repeatedly passed through for 30 times to obtain a nano-fibrillated material having a width of 300 nm or less , A synthetic composite of nanocellulose and calcium carbonate was prepared in a weight ratio of 1:30 by the same method as in Example 1. [

Comparative Example  4

In Example 3 (b), 30% by weight of heavy calcium carbonate (GCC) having an average size of 2 to 3 탆 was added to prepare a paper having a basis weight of 60 g / m ² instead of the synthetic composite of fine powder and calcium carbonate.

Comparative Example  5

In Comparative Example 4, paper having a basis weight of 60 g / m ² was prepared in the same manner as in Comparative Example 4, except that 40% by weight of heavy calcium carbonate (GCC) was added.

Comparative Example  6

In the b) of Example 3, a paper having a basis weight of 60 g / m ² was prepared in the same manner as in Example 3, except that the microfine particle and calcium carbonate synthesis composite prepared in Comparative Example 1 were used.

Comparative Example  7

In Comparative Example 6, paper having a basis weight of 60 g / m ² was prepared in the same manner as in Comparative Example 6, except that 40% by weight of a synthetic composite of a fine powder and calcium carbonate was used.

Comparative Example  8

In the b) of Example 3, a paper having a basis weight of 60 g / m ² was prepared in the same manner as in Example 3, except that the microfine particle and calcium carbonate synthesis composite prepared in Comparative Example 2 were used.

Comparative Example  9

In Comparative Example 8, paper having a basis weight of 60 g / m ² was prepared in the same manner as in Comparative Example 8, except that 40% by weight of a synthetic composite of a fine powder and calcium carbonate was used.

Comparative Example  10

In the b) of Example 3, a paper having a basis weight of 60 g / m ² was prepared in the same manner as in Example 3, except that the composite of nanocellulose and calcium carbonate prepared in Comparative Example 3 was used.

Comparative Example  11

In Comparative Example 10, paper having a basis weight of 60 g / m ² was prepared in the same manner as in Comparative Example 10, except that 40% by weight of the synthetic complex of nanocellulose and calcium carbonate was used.

Test Example  One

The papers produced in Examples 3 to 6 and Comparative Examples 4 to 11 were measured by ISO standard test method and Tappi standard test method. The measurement items were heat-shrinkage (ISO 1924-1), bulk (ISO 534) (ISO 5626), smoothness (ISO 5627), flexural stiffness (Tappi T 566), filler content (ash measurement, Tappi T 211)

As shown in Table 1, a synthetic composite of fine powder and calcium carbonate was formed at 40 占 폚. Examples 3 and 4, in which the weight ratio of fine powder: calcium carbonate was 1:30, and the weight ratio of fine powder: calcium carbonate, Compared to Examples 5 and 6 having a ratio of 1:50, a remarkably high heat shrinkage was exhibited as compared with Comparative Examples 6 to 9 in which the same proportion of filler was contained and the calcium silicate composite was formed at 20 DEG C, Very high flexural stiffness and bending strength. Practically, Comparative Examples 6 to 9 lacked all strength properties and bending stiffness to the extent that it was difficult to use as printing paper.

In Comparative Examples 4 and 5, paper prepared by using heavy calcium carbonate (GCC), which is mainly used in the papermaking process, in place of the microparticles and the calcium carbonate composite composite of the present invention, It was confirmed that the heat shrinkage of Comparative Examples 4 and 5 was about 30 to 40% lower and the flexural stiffness was about 15 to 40% lower than that of the paper sheets.

On the other hand, in Comparative Example 10 and Comparative Example 11 in which the nanocellulose and the calcium carbonate synthesis composite of Comparative Example 3 using nanocellulose were used, the heat shrinkage and bulk were similar to those of Examples 3 to 6 of the present invention But the level of smoothness was very low. Especially, in the case of printing paper using a lot of calcium carbonate, smoothness is most important for excellent printing, which is significantly lower than those of Examples 3 to 6 according to the present invention and lower than those of Comparative Examples 4 to 5 made of heavy calcium carbonate appear. Thus, it can be seen that the paper according to the present invention has excellent smoothness.

Filler
Kinds Filler content
(weight%) Heat gauge
(km) bulk
(cm < ³ > / g) Smoothness
Top side
(seconds) Flexural Stiffness
(gcm) My theft
(Number of times) Example 3 Example 1 30 2.37 1.90 5.6 25.0 28.7 Example 4 Example 1 40 2.07 1.86 6.3 21.7 13.8 Example 5 Example 2 30 2.29 1.86 7.9 20.4 27.8 Example 6 Example 2 40 1.95 1.83 8.3 19.6 9.2 Comparative Example 4 Heavy calcium carbonate (GCC) 30 1.66 1.86 3.9 17.6 8.3 Comparative Example 5 Heavy calcium carbonate (GCC) 40 1.39 1.81 5.0 16.9 3.3 Comparative Example 6 Comparative Example 1 30 1.62 1.54 15.3 14.1 1.8 Comparative Example 7 Comparative Example 1 40 0.91 1.47 21.3 9.7 0.0 Comparative Example 8 Comparative Example 2 30 1.33 1.61 10.6 12.7 1.0 Comparative Example 9 Comparative Example 2 40 0.93 1.54 14.6 8.6 0.0 Comparative Example 10 Comparative Example 3 30 2.52 1.90 2.5 18.3 15.8 Comparative Example 11 Comparative Example 3 40 1.98 1.83 1.8 17.5 11.0

Claims (10)

(1) fibrillating wood fibers, non-wood fibers or mixtures thereof with a refiner;
(2) passing the fibrillated fiber through a screen to obtain microfine cellulose fine particles having a water standard value of not more than 200 ml and a water retention value of not less than 1.5 g / g of WRV;
(3) preparing the fine particles in a solution of 0.2 to 4.0% by weight, adding a calcium compound to the solution and mixing the solution;
(4) adding an ionic polymer to the solution of the fine particles mixed with the calcium compound to prepare a fine particle and a calcium compound complex; And
(5) A method for producing a filler, comprising the steps of: injecting carbon dioxide into the above-mentioned fine powder and calcium compound composite at 30 to 60 ° C to prepare a synthetic composite of fine powder and calcium carbonate. 2. The method according to claim 1, wherein in step (1), the wood fiber is chemical pulp of a softwood, a hardwood or a mixture thereof, and the non-wood fiber is selected from the group consisting of Abaca pulp, Rice straw pulp, Red algae pulp, Vargas pulp, Wherein the chemical pulp is at least one selected from cotton pulp, mar pulp, jute pulp and kenya pulp. The method of claim 1, wherein in step (2), the screen is a 100 to 500 mesh screen. The method according to claim 1, wherein in step (3), the calcium compound is at least one selected from calcium hydroxide, calcium chloride, calcium sulfate and calcium phosphate. The method according to claim 1, wherein the mixing ratio of the fine powder and the calcium compound in the step (3) is 1: 1 to 1:70. The method according to claim 1, wherein the average particle size of the microparticulate and calcium compound composites prepared in step (4) is 5 to 50 μm. The method of claim 1, wherein the ionic polymer in step (4) is a cationic, anionic, or nonionic polymer. The method of claim 7, wherein the cationic polymer is selected from the group consisting of polyacryl amide, polydadmac, polydiallyldimethylammonium chloride, cationic starch, polyethyleneimine, or polyamine Characterized in that the anionic polymer is a polyacrylamide, a micro polymer or an anionic starch, and the nonionic polymer is polyethylene oxide, starch or guar gum. A paper comprising a filler produced by the process according to any one of claims 1 to 8. 10. The paper of claim 9, wherein the paper comprises from 10 to 60% by weight filler.

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